CN103058182A - Method for preparing graphene by solution phase - Google Patents
Method for preparing graphene by solution phase Download PDFInfo
- Publication number
- CN103058182A CN103058182A CN2013100313622A CN201310031362A CN103058182A CN 103058182 A CN103058182 A CN 103058182A CN 2013100313622 A CN2013100313622 A CN 2013100313622A CN 201310031362 A CN201310031362 A CN 201310031362A CN 103058182 A CN103058182 A CN 103058182A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite
- solution phase
- powder
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for preparing graphene by a solution phase, and relates to grephene. The invention provide a method for preparing graphene by the solution phase, which is low in cost, simple and easy to implement, low in device requirements, and beneficial to large-scale industrial production. The method comprises the following steps: (1) adding graphite powder to a tetrahydrofuran solution and obtaining graphite-powder tetrahydrofuran dispersion liquid by carrying out ultrasonic dispersion under the protection of nitrogen gas; (2) adding alkali metal and naphthalene to the graphite-powder tetrahydrofuran dispersion liquid obtained in the step (1), stirring under the protection of the nitrogen gas to obtain the mixed solution; (3) adding halogenated organic reagent to the mixed solution obtained in the step (2), and reacting under the protection of the nitrogen gas to obtain a solid product; and (4) washing and drying the solid product obtained in the step (3) to obtain the graphene powder. According to the method disclosed by the invention, liquid-phase chemical intercalation is carried out to the graphite by using the graphite powder as material; and then, the chemical modification of the halogenated organic reagent to the graphite is utilized for further opening the graphite, so that the graphene can be prepared by peeling the graphite under the non-ultrasonic action or the light ultrasonic action.
Description
Technical field
The present invention relates to Graphene, especially relate to the method that a kind of solution phase prepares Graphene.
Background technology
Graphene is a kind of fully by sp
2What the hydridization carbon atom consisted of only is the New Two Dimensional carbon material of monatomic thickness.Since 2004 are prepared first, Graphene is just paid close attention to widely with its unique structure and excellent character, such as high-specific surface area, high charge mobility, high strength and snappiness, high thermal conductivity coefficient etc., be expected to obtain widespread use in energy and material, nano electron device, matrix material, photoelectric device, sensor field.
Graphene be at first by the micromechanics stripping method from highly oriented pyrolytic graphite separate (Novoselov K S etc., Science, 2004,306:666-669), but the method output is little, is only applicable to fundamental research.The low cost of Graphene, extensive preparation are still the key issue of this Materials of restriction and application.Based on Hummers method (Hummers W S etc., J.Am.Chem.Soc.80,1339) chemical oxidization method is a kind of graphene preparation method (the Stankovich S etc. that are widely adopted at present, Carbon45,1558-1565), the method is carried out oxide treatment with graphite, obtains graphite oxide, and then it is carried out ultrasonic peeling off obtains graphene oxide.The method cost is low, output is large, but since oxidising process can havoc the laminated structure of Graphene introduce many defectives, even process through chemical reduction and thermal reduction, the property indices of gained Graphene, still unsatisfactory such as electroconductibility etc.As carbon source, at the chemical Vapor deposition process of the pyrolytic decomposition growing graphene of substrate surface at present also be applied to the preparation (Sutter P W etc., Nat.Mater.7,406-411) of Graphene by it with carbon compounds such as methane.The Graphene area that this method prepares is larger, but often needs complicated equipment, and processing condition are harsh, are difficult to extensive preparation.Except above-mentioned these methods, silicon carbide epitaxial growth method (Berger C etc., Science, 312,1191-1196), organic synthesis method (Zhi L J etc., J.Mater.Chem.18,1472-1484) etc. also is applied to the preparation of Graphene, but all there is the drawback of self in these methods, as complex process be difficult to control, yield poorly, high in cost of production.Therefore, exploitation a kind of can be on a large scale, that low cost prepares the method for Graphene is very necessary.
Summary of the invention
The object of the present invention is to provide low-costly, simple, not high to equipment requirements, be beneficial to the method that a kind of solution phase that large-scale industrialization produces prepares Graphene.
The present invention includes following steps:
1) Graphite Powder 99 is added in the tetrahydrofuran solution, under the nitrogen protection condition, carry out ultra-sonic dispersion and get Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid;
2) in step 1) gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, add successively basic metal and naphthalene, under nitrogen protection, stir, get mixing solutions;
3) in step 2) add the halo organic reagent in the mixing solutions of gained, under the nitrogen protection condition, react, get solid product;
4) with the washing of step 3) gained solid product, drying obtains graphene powder.
In step 1), described Graphite Powder 99 can adopt common commercially available Graphite Powder 99; It is the ultrasonic processor of 90W that described ultra-sonic dispersion can adopt equipower, and ultrasonic time can be 3min.
In step 2) in, described basic metal can adopt metallic lithium or sodium Metal 99.5 etc.; Graphite (carbon atom) and alkali-metal mol ratio can be 1 in the described Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid: (4～30), the mol ratio of basic metal and naphthalene can 1; The time of described stirring can be 30～120min.
In step 3), described halo organic reagent can be selected from a kind of in halogenated alkane, halogenated carboxylic acid (salt), halogenated carboxylic ester, halogen ester, halohydrin, halogenated amine, halogen acid amide, the halo ammonium salt etc.; Described halo organic reagent and alkali-metal mol ratio can be 1: 1; The time of described reaction can be 5～24h, and the molecular formula of described halogenated alkane is X (CH
2)
nCH
3, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halogenated carboxylic acid (salt) is X (CH
2)
nCOOR, wherein X is halogen atom, n is integer, 1＜n＜20, R is H or Na, K; The molecular formula of described halogenated carboxylic ester is X (CH
2)
nCOOR, wherein X is halogen atom, n is integer, 1＜n＜20, R is CH
3Or C
2H
5The molecular formula of described halohydrin is X (CH
2)
nOH, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halo aliphatic amide is X (CH
2)
nNH
2, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halogen acid amide is X (CH
2)
nCONH
2, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halo ammonium salt is X (CH
2)
nN
+R
3Br
-, wherein X is halogen atom, n is integer, and 1＜n＜20, R is CH
3Or C
2H
5
In step 4), described washing can be washed with ethanol, toluene, water and ethanol successively, and described drying can be dry under 60 ° of C vacuum conditions; The number of plies of described graphene powder can be below 5 layers, preferred single layer.
The present invention carries out the liquid phase chemical intercalation take Graphite Powder 99 as raw material with graphite, then utilizes the halo organic reagent that the chemical modification of graphite is further strutted graphite, graphite can be peeled off under not ultrasonic or slight ultrasonication and prepare Graphene.
Compare with existing graphene preparation method, beneficial effect of the present invention is as follows:
(1) Graphene that obtains of the present invention oxidising process of not passing through strong oxidizer, graphene film layer defects still less, quality is higher, and all operations all carries out under room temperature, solution phase condition, preparation method's energy consumption is low, efficient is high.The Graphene that obtains like this has dispersed preferably in the aqueous solution or organic solvent (such as chloroform, DMF (DMF), ethanol, chlorobenzene etc.), and the intercalation compound dispersion of formation and the degree of intercalation are higher.
(2) the halo organic reagent further enlarges the interlamellar spacing of graphite among the present invention to the chemical modification of graphite intercalation compound, does not need ultrasonic or short period of time, low power ultrasound can be realized peeling off of Graphene.
(3) intercalation of graphite and chemical modification are all finished at solution phase among the present invention, the completeness of reaction and good uniformity, and the efficient of preparation is high.
(4) all operations of the present invention is all at room temperature finished, and Graphene preparation technology energy consumption is low.
(5) preparation technology of the present invention is simple, and is low to the production unit requirement, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the macro morphology figure (sample quality is respectively 10mg) of commercially available Graphite Powder 99 (a) and gained graphene powder of the present invention (b).
Fig. 2 is the scanning electron microscope diagram of gained Graphene of the present invention.In Fig. 2, scale is 1.00 μ m.
Fig. 3 is the transmission electron microscope figure of gained Graphene of the present invention.In Fig. 3, scale is 200nm.
Fig. 4 is the Raman spectrogram of gained Graphene of the present invention.In Fig. 4, X-coordinate is Raman shift Raman shift(cm
-1), ordinate zou is intensity I ntensity(a.u.)
Fig. 5 is the dispersion liquid figure of gained Graphene of the present invention in chloroform.
Embodiment
Embodiment 1
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that the 150mL fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in this dispersion liquid, continues to stir 35min.In said mixture, progressively add the 12.5g1-bromododecane, under the nitrogen protection condition, continue reaction 12h.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water and washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Fig. 1 b is the macro morphology figure of gained graphene powder of the present invention, compares with the commercially available Graphite Powder 99 of Fig. 1 a to present obvious puffy.With gained Graphene of the present invention scanning electronic microscope and transmission electron microscope observation, gained as shown in Figures 2 and 3.As can be seen from Figure 2, be stripped from out after the chemical modification of graphite through liquid phase intercalation and halo organic reagent, fold appears in the Graphene surface.Fig. 3 is the transmission electron microscope figure of gained graphene film, can clearly find out the Graphene profile.Fig. 4 is the Raman spectrogram of gained Graphene of the present invention, can find out, the 2D peak is unimodal, and intensity is significantly higher than the G peak, has the Raman spectrum characteristic of single-layer graphene.Fig. 5 is the chloroform dispersion liquid of gained Graphene of the present invention.
Embodiment 2
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in mixed solution, continues to stir 35min.In said mixture, progressively add the 9.7g6-bromocaproic acid, under the nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water and washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.The gained graphene powder can be scattered in ethanol or the aqueous solution by supersound process.
Embodiment 3
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in mixed solution, continues to stir 35min.In said mixture, progressively add 11.6g6-bromocaproic acid methyl esters, under the nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 4
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in mixed solution, continues to stir 35min.In said mixture, progressively add 11.2g9-bromine nonyl alcohol, under the nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 5
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in mixed solution, continues to stir 35min.In said mixture, progressively add 9.7g6-bromohexane acid amides, under the nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 6
The 100mg Graphite Powder 99 is added the tetrahydrofuran solution that fresh dried is crossed, and then ultra-sonic dispersion 3min under the nitrogen protection condition adds 0.36g metallic lithium and 4.9g naphthalene successively in mixed solution, continues to stir 20min.In said mixture, progressively add 14.5g(5-bromine amyl group) trimethylammonium bromide, react 12h under the nitrogen protection condition.
In above-mentioned reaction product, add ethanol to remove completely metallic lithium of unreacted.The gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Claims (10)
1. a solution phase prepares the method for Graphene, it is characterized in that may further comprise the steps:
1) Graphite Powder 99 is added in the tetrahydrofuran solution, under the nitrogen protection condition, carry out ultra-sonic dispersion and get Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid;
2) in step 1) gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, add successively basic metal and naphthalene, under nitrogen protection, stir, get mixing solutions;
3) in step 2) add the halo organic reagent in the mixing solutions of gained, under the nitrogen protection condition, react, get solid product;
4) with the washing of step 3) gained solid product, drying obtains graphene powder.
2. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 1), and described ultra-sonic dispersion is that to adopt equipower be the ultrasonic processor of 90W, and ultrasonic time is 3min.
3. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 2) in, described basic metal adopts metallic lithium or sodium Metal 99.5.
4. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 2) in, graphite and alkali-metal mol ratio are 1: 4～30 in the described Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, the mol ratio of basic metal and naphthalene〉1.
5. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 2) in, the time of described stirring is 30～120min.
6. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 3), described halo organic reagent is selected from a kind of in halogenated alkane, halogenated carboxylic acid (salt), halogenated carboxylic ester, halogen ester, halohydrin, halogenated amine, halogen acid amide, the halo ammonium salt.
7. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 3), and described halo organic reagent and alkali-metal mol ratio are 1: 1; The time of described reaction is 5～24h.
8. a kind of solution phase prepares the method for Graphene as claimed in claim 6, and the molecular formula that it is characterized in that described halogenated alkane is X (CH
2)
nCH
3, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halogenated carboxylic acid (salt) is X (CH
2)
nCOOR, wherein X is halogen atom, n is integer, 1＜n＜20, R is H or Na, K; The molecular formula of described halogenated carboxylic ester is X (CH
2)
nCOOR, wherein X is halogen atom, n is integer, 1＜n＜20, R is CH
3Or C
2H
5The molecular formula of described halohydrin is X (CH
2)
nOH, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halo aliphatic amide is X (CH
2)
nNH
2, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halogen acid amide is X (CH
2)
nCONH
2, wherein X is halogen atom, n is integer, 1＜n＜20; The molecular formula of described halo ammonium salt is X (CH
2)
nN
+R
3Br
-, wherein X is halogen atom, n is integer, and 1＜n＜20, R is CH
3Or C
2H
5
9. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 4), and described washing is washed with ethanol, toluene, water and ethanol successively, and described drying is dry under 60 ° of C vacuum conditions.
10. a kind of solution phase prepares the method for Graphene as claimed in claim 1, it is characterized in that in step 4), and the number of plies of described graphene powder is below 5 layers, preferred single layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310031362.2A CN103058182B (en) | 2013-01-27 | 2013-01-27 | Method for preparing graphene by solution phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310031362.2A CN103058182B (en) | 2013-01-27 | 2013-01-27 | Method for preparing graphene by solution phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103058182A true CN103058182A (en) | 2013-04-24 |
| CN103058182B CN103058182B (en) | 2014-10-08 |
Family
ID=48101124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310031362.2A Active CN103058182B (en) | 2013-01-27 | 2013-01-27 | Method for preparing graphene by solution phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103058182B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253659A (en) * | 2013-05-23 | 2013-08-21 | 渤海大学 | Method for preparing graphene through carrying out ultrasonic stripping on graphite |
| CN103555326A (en) * | 2013-10-17 | 2014-02-05 | 厦门大学 | Preparation method of oxygen-free graphene fluorescence quantum dots |
| CN104229775A (en) * | 2013-06-21 | 2014-12-24 | 厦门大学 | Method for preparing graphene fluorescent nano material |
| CN104891460A (en) * | 2015-05-29 | 2015-09-09 | 厦门大学 | Method for preparing graphite-phase carbon nitride nanosheets by using solution phase |
| CN107986268A (en) * | 2017-12-13 | 2018-05-04 | 天津宝兴威科技股份有限公司 | A kind of preparation method of alkyl functional graphite alkene quantum dot |
| CN108690678A (en) * | 2018-06-01 | 2018-10-23 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the lubricating oil of graphene-containing |
| CN111542953A (en) * | 2018-01-26 | 2020-08-14 | 株式会社Lg化学 | Conductive agent, slurry for forming electrode including the same, electrode, and lithium secondary battery manufactured using the same |
| CN112620643A (en) * | 2020-11-20 | 2021-04-09 | 浙江南都电源动力股份有限公司 | Preparation method of graphene-coated lithium metal |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276885B (en) * | 2016-10-21 | 2018-07-13 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433823A (en) * | 2008-11-28 | 2009-05-20 | 江苏工业学院 | Method for preparing CTAB modified expanded graphite and use in absorbing formaldehyde gas |
-
2013
- 2013-01-27 CN CN201310031362.2A patent/CN103058182B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433823A (en) * | 2008-11-28 | 2009-05-20 | 江苏工业学院 | Method for preparing CTAB modified expanded graphite and use in absorbing formaldehyde gas |
Non-Patent Citations (1)
| Title |
|---|
| 肖敏等: "三元型钾-四氢呋喃-GIC的制备及稳定性研究", 《新型炭材料》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253659A (en) * | 2013-05-23 | 2013-08-21 | 渤海大学 | Method for preparing graphene through carrying out ultrasonic stripping on graphite |
| CN103253659B (en) * | 2013-05-23 | 2015-09-23 | 渤海大学 | A kind of ultrasonic wave peels off the method for preparing graphite alkene |
| CN104229775A (en) * | 2013-06-21 | 2014-12-24 | 厦门大学 | Method for preparing graphene fluorescent nano material |
| CN103555326A (en) * | 2013-10-17 | 2014-02-05 | 厦门大学 | Preparation method of oxygen-free graphene fluorescence quantum dots |
| CN103555326B (en) * | 2013-10-17 | 2015-09-23 | 厦门大学 | A kind of preparation method of oxygen-free Graphene fluorescence quantum |
| CN104891460A (en) * | 2015-05-29 | 2015-09-09 | 厦门大学 | Method for preparing graphite-phase carbon nitride nanosheets by using solution phase |
| CN107986268A (en) * | 2017-12-13 | 2018-05-04 | 天津宝兴威科技股份有限公司 | A kind of preparation method of alkyl functional graphite alkene quantum dot |
| CN111542953A (en) * | 2018-01-26 | 2020-08-14 | 株式会社Lg化学 | Conductive agent, slurry for forming electrode including the same, electrode, and lithium secondary battery manufactured using the same |
| CN108690678A (en) * | 2018-06-01 | 2018-10-23 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the lubricating oil of graphene-containing |
| CN108690678B (en) * | 2018-06-01 | 2021-10-29 | 湖南国盛石墨科技有限公司 | Preparation method of lubricating oil containing graphene |
| CN112620643A (en) * | 2020-11-20 | 2021-04-09 | 浙江南都电源动力股份有限公司 | Preparation method of graphene-coated lithium metal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103058182B (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103058182B (en) | Method for preparing graphene by solution phase | |
| Zhang et al. | Graphene nanosheets synthesis via chemical reduction of graphene oxide using sodium acetate trihydrate solution | |
| CN103408000B (en) | Preparation method for oxidized grapheme in large sheet | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| CN102698666B (en) | Based on the preparation method of the graphene/nanometer particle composite material of infrared irridiation | |
| CN104891479B (en) | Plant-based graphene and preparation method thereof | |
| Yan et al. | A simple and fast microwave assisted approach for the reduction of graphene oxide | |
| CN103337611A (en) | Preparation method of graphene-titanium dioxide composite material | |
| Liu et al. | The preparation of holey phosphorene by electrochemical assistance | |
| CN103787288B (en) | A kind of preparation method of boron nitride alkene nanometer sheet | |
| CN102583324B (en) | Preparation method of amorphous state carbon nano tube | |
| CN102464312B (en) | Preparation method of graphene | |
| Kumar et al. | Surface modification of graphene oxide using esterification | |
| CN106276885B (en) | The fast preparation method of high conductivity nitrogen-doped graphene | |
| Krishna et al. | Improved reduction of graphene oxide | |
| CN103420361A (en) | A method of preparing graphene by explosion | |
| CN106082194B (en) | A kind of method for preparing bigger serface and the less graphene of the number of plies | |
| CN107140623B (en) | A method of preparing graphene | |
| Yang et al. | Graphene supported chromium carbide material synthesized from Cr-based MOF/graphene oxide composites | |
| CN103130214A (en) | Method of preparing graphene through chemical reduction method | |
| CN104528737B (en) | Preparation method of a kind of nano level stratiform silicon-dioxide/graphene composite material and products thereof | |
| Lu et al. | Controllable synthesis of spindle-like ZnO nanostructures by a simple low-temperature aqueous solution route | |
| CN106672957A (en) | Method for preparing graphene oxide according to Fenton oxidation method | |
| CN103387228B (en) | Preparation method for graphene scrolls | |
| CN106587020A (en) | Quick preparation method of high-conductivity sulfur-doped graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 363000 the southern tip of Xiamen University Zhangzhou campus, Zhangzhou, Fujian Patentee after: XIAMEN University Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: XIAMEN University |